U.S. patent number 5,543,513 [Application Number 08/393,245] was granted by the patent office on 1996-08-06 for trehalose desiccant product and dehydration therewith.
This patent grant is currently assigned to Kabushiki Kaisha Hayashibara, Seibutsu Kagaku Kenkyujo. Invention is credited to Takahiko Mandai, Toshio Miyake, Takashi Shibuya, Toshiyuki Sugimoto.
United States Patent |
5,543,513 |
Mandai , et al. |
August 6, 1996 |
Trehalose desiccant product and dehydration therewith
Abstract
Disclosed are a novel desiccant containing a non-reducing
anhydrous trehalose as an effective ingredient; a dehydration of
hydrous matters, e.g. food products, pharmaceuticals and cosmetics,
therewith; and dehydrated products obtained by the dehydration.
Such hydrous matters are dehydrated without causing alteration or
deterioration by incorporating anhydrous trehalose into the hydrous
matters to convert the anhydrous trehalose into hydrous crystalline
trehalose. The anhydrous trehalose are anhydrous crystalline
trehalose and hydrous amorphous trehalose.
Inventors: |
Mandai; Takahiko (Okayama,
JP), Shibuya; Takashi (Okayama, JP),
Sugimoto; Toshiyuki (Okayama, JP), Miyake; Toshio
(Okayama, JP) |
Assignee: |
Kabushiki Kaisha Hayashibara
(Okayama, JP)
Seibutsu Kagaku Kenkyujo (Okayama, JP)
|
Family
ID: |
26580465 |
Appl.
No.: |
08/393,245 |
Filed: |
February 23, 1995 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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159600 |
Dec 1, 1993 |
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Current U.S.
Class: |
536/123.13;
252/194; 426/443 |
Current CPC
Class: |
C12G
3/005 (20130101); A23L 11/50 (20210101); A23L
3/3562 (20130101); A61K 9/0014 (20130101); A61K
9/0019 (20130101); A23L 3/3427 (20130101); A23L
15/20 (20160801); B01J 20/22 (20130101); A23C
9/1232 (20130101); A23L 15/30 (20160801); A61K
47/26 (20130101); A61Q 19/00 (20130101); A61Q
11/00 (20130101); A23L 3/42 (20130101); A23L
19/105 (20160801); A61K 8/60 (20130101); A61Q
7/00 (20130101); A61Q 5/00 (20130101) |
Current International
Class: |
A23C
9/123 (20060101); A23L 1/20 (20060101); A23L
1/214 (20060101); A23C 9/12 (20060101); A23L
1/32 (20060101); A23L 3/3463 (20060101); A23L
3/34 (20060101); A23L 3/3562 (20060101); A23L
3/40 (20060101); A23L 3/3427 (20060101); A23L
3/42 (20060101); C12G 3/00 (20060101); A61K
47/26 (20060101); B01J 20/22 (20060101); C07H
003/06 () |
Field of
Search: |
;514/53 ;536/123.13
;252/194 ;426/443 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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486315A2 |
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Nov 1991 |
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EP |
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15253687 |
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Dec 1985 |
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JP |
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15253787 |
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Dec 1985 |
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JP |
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13624087 |
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Dec 1985 |
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JP |
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17949092 |
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Nov 1990 |
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JP |
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Other References
Hakko-Kyokai-Shi, vol. 17., pp. 106-115 (1959). .
Journal of the Chemical Society, pp. 3489-3490 (1965). .
Jeffrey et al. Carbohydr. Res. 1985, 137, 21-30. .
Levine et al. BioPharm May 1992, 5(4), 36-40..
|
Primary Examiner: Robinson; Douglas W.
Assistant Examiner: Fonda; Kathleen Kahler
Attorney, Agent or Firm: Browdy and Neimark
Parent Case Text
This application is a continuation of application Ser. No.
08/159,600, filed Dec. 1, 1993, now abandoned.
Claims
We claim:
1. In a desiccant comprising a saccharide as an the dessicant
ingredient and an inert diluent, the improvement wherein said
saccharide is selected from the group consisting of anhydrous
crystalline trehalose, anhydrous amorphous trehalose and mixtures
thereof, which anhydrous trehalose has substantially no reducing
activity and which is converted into hydrous crystalline trehalose
upon absorbing moisture, and wherein said anhydrous crystalline
trehalose is obtained by:
providing a syrupy aqueous solution of trehalose with a moisture
content lower than 10 w/w %;
maintaining said syrupy aqueous solution of trehalose at a
temperature in the range of 50.degree.-160.degree. C. in the
presence of a seed crystal in order to crystallize anhydrous
crystalline trehalose; and
recovering the resultant anhydrous crystalline trehalose; and
said anhydrous amorphous trehalose is obtained by drying a syrupy
aqueous solution of trehalose or a hydrous crystalline trehalose,
and recovering the resultant anhydrous amorphous trehalose.
2. A method for dehydrating a hydrous matter comprising adding from
0.01 to 200 parts by weight of anhydrous trehalose to one part by
weight of a hydrous matter to convert said anhydrous trehalose into
hydrous crystalline trehalose, thereby dehydrating said hydrous
matter, wherein said anhydrous trehalose is selected from the group
consisting of anhydrous crystalline trehalose, anhydrous amorphous
trehalose, and mixtures thereof;
wherein said anhydrous crystalline trehalose is obtained by:
providing a syrupy aqueous solution of trehalose with a moisture
content lower than 10 w/w %;
maintaining said syrupy aqueous solution of trehalose at a
temperature in the range of 50.degree.-160.degree. C. in the
presence of a seed crystal in order to crystallize anhydrous
crystalline trehalose; and
recovering the resultant anhydrous crystalline trehalose; and
said anhydrous amorphous trehalose is obtained by drying a syrupy
aqueous solution of trehalose or a hydrous crystalline trehalose,
and recovering the resultant anhydrous amorphous trehalose.
3. The method of claim 2 wherein said hydrous matter contains at
least one member selected from the group consisting of gelatinized
starch, alcohols, oil-soluble substances and biologically active
substances.
4. The method of claim 2 wherein said anhydrous trehalose entraps
about 10 w/w % moisture from said hydrous matter.
Description
FIELD OF THE INVENTION
The present invention relates to a desiccant comprising anhydrous
trehalose as an effective ingredient, as well as to a method for
dehydrating hydrous matters with said desiccant and to dehydrated
products obtainable by the method.
DEFINITION
Throughout the specification, the wording "w/w %" will be
abbreviated as "%", unless specified otherwise.
BACKGROUND OF THE INVENTION
As disclosed by the present inventors in Japanese Patent Laid-Open
Nos.136,240/87, 152,536/87 and 152,537/87, conventional dehydration
methods using anhydrous saccharides are those wherein a dehydrating
activity is utilized, said activity being exerted by allowing an
anhydrous saccharide to absorb moisture from a hydrous matter to
convert the anhydrous saccharide into a hydrous crystalline form.
Unlike heat drying, these methods require no heating conditions and
have a merit of converting hydrous matters into dehydrated products
without deterioration or degeneration of their quality.
It was found that among the above-mentioned methods the method
using anhydrous aldohexoses such as anhydrous glucose or galactose
as disclosed in Japanese Patent Laid-Open No.152,536/87, attains a
satisfiable dehydration of a relatively-large amount of water and
readily induces the maillard reaction because such an anhydrous
aldohexose has a reducing property and a relatively-high reactivity
to substances such as amino acids or peptides; and because of
these, there exists an anxiety about the stability of the resultant
dehydrated product. It was also found that anhydrous aldohexoses
are not convertible into hydrous crystalline aldohexoses even at an
elevated humid condition, and only exert a poor
dehydrating-activity. It was found that in case of using anhydrous
maltose as disclosed in Japanese Patent Laid-Open No. 136,240/87
and in case of using anhydrous paratinose as disclosed in Japanese
Patent Laid-Open No. 152,537/87, there still remains an anxiety
about a long-term stability of the resultant dehydrated product
because anhydrous maltose and anhydrous paratinose, even if they
have a relatively-low reducing activity, are basically reducing
sugars. It was also found that the amount of moisture absorbed by
anhydrous maltose or anhydrous paratinose is relatively low, i.e.
about 5 w/w % with respect to the amount of the anhydrous maltose
or the anhydrous paratinose, and because of this such saccharides
have a demerit that it should be used as a desiccant in a
relatively-large amount.
It may be speculated that anhydrous non-reducing
glycosylfructosides such as anhydrous raffinose, anhydrous erlose
and anhydrous melezitose as disclosed in Japanese Patent Laid-Open
No. 152,537/87 have no reducing activity and do not react with
amino acids and peptides, and this imparts them a satisfactory
shelf-life without inducing the maillard reaction. Anhydrous
glycosylfructosides, however, have a fructoside bond with a
relatively-low acid tolerance in their molecules, and this may lead
to an estimation that the anhydrous glycosylfructosides are not
necessarily suitable as a desiccant for acid hydrous matters. In
this case, there still remains an anxiety about stability in the
resultant dehydrated products.
SUMMARY OF THE INVENTION
In order to overcome these demerits of conventional dehydration
methods using saccharides, the present inventors have screened
natural non-reducing anhydrous saccharides and studied to establish
a desiccant with a satisfiable dehydrating activity, as well as its
uses.
As a result, the present inventors found that among the
non-reducing anhydrous saccharides as tested anhydrous trehalose
(throughout the specification, ".alpha., .alpha.-trehalose" and
".alpha.,.beta.-trehalose" are designated as "trehalose" and
"neotrehalose" respectively) dehydrates a relatively-large amount
of water and exerts a strong dehydrating activity, and that the
resultant dehydrated products prepared with the anhydrous trehalose
are extremely stable. These render the anhydrous trehalose useful
as a desiccant in a variety of fields. In other words, the present
inventors found that when anhydrous trehalose is incorporated into
hydrous matters such as hydrous food-products and hydrous
pharmaceuticals, the anhydrous trehalose is converted into hydrous
crystalline trehalose which absorbs a relatively-large amount of
water in the hydrous matters and exerts as a desiccant a strong
dehydrating-activity. The anhydrous trehalose is used in a variety
of hydrous matters including hydrous acidic matters. The present
inventors also confirmed that anhydrous trehalose is used in the
preparation of dehydrated products such as dehydrated food products
with a satisfactory taste and quality, as well as dehydrated
pharmaceuticals with a relatively-high activity and stability.
Thus, the present inventors accomplished this invention.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 shows a powder x-ray diffraction figure of hydrous
crystalline trehalose.
FIG. 2 shows a powder x-ray diffraction figure of anhydrous
crystalline trehalose.
FIG. 3 shows a powder x-ray diffraction figure of anhydrous
amorphous trehalose.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventors screened desiccants using non-reducing
saccharides and chose as the desiccant anhydrous trehalose which
had not been deemed useful for that purpose. The present inventors
first accomplished the dehydration method for a hydrous matter by
incorporating anhydrous trehalose thereinto.
The dehydration method according to the present invention can be
arbitrarily used to dehydrate hydrous matters, especially, those
which contain free water different from a bonded water such as
water incorporated in a crystalline structure. For example, the
present method can be advantageously used to decrease the moisture
content in atmosphere of a moistureproof package enclosing a
dehydrated food product, as well as to decrease the moisture
content in a variety of hydrous matters such as food products,
pharmaceuticals, cosmetics, chemicals for industrial uses, and
their materials or intermediates.
The present inventors found that when anhydrous trehalose is
incorporated into the above-mentioned hydrous matters, it entraps
about 10 w/w % moisture from the hydrous matters in hydrous
crystalline trehalose, which is 2-fold higher than that attained
with anhydrous maltose, and substantially eliminates the moisture
from the hydrous matters or even brings them to dryness.
It was also found that the relative humidity in a moistureproof
package enclosing a dehydrated food product, for example,
"ajitsuke-nori" (seasoned laver) and cookie, is extremely decreased
by placing in the moistureproof package a small moisture-permeable
paper-bag injected with anhydrous trehalose, whereby the quality of
the dehydrated food product or powdery product is stabilized over a
relatively-long period of time.
Since anhydrous trehalose neither becomes sticky nor oozes during
or after conversion into hydrous crystalline trehalose, dehydrated
food products and moistureproof packages are free from staining.
Anhydrous trehalose prevents the solidification of powdery products
and their adhesion to moistureproof packages. In addition,
trehalose per se causes no side effect because it is a non-toxic
and harmless natural-sweetener.
According to the present invention, high-quality food products with
a substantially-decreased moisture in the form of, for example,
massecuite or powder, can be readily prepared by incorporating
anhydrous trehalose into food products with a relatively-high
moisture content in liquid or paste form, for example, brandy,
vinegar, royal jelly, fresh cream and mayonnaise to convert the
anhydrous trehalose into hydrous crystalline trehalose.
The dehydration method according to the present invention is
characterized in that it utilizes a stable non-reducing saccharide,
i.e. anhydrous trehalose, and requires no heat treatment such as
heat drying, whereby a relatively-high moisture content food
product in liquid or paste form is readily converted into a
dehydrated product with a decreased moisture and a satisfiable
flavor and taste without alternating or deteriorating the food
product.
It was found that dehydrated food products in which anhydrous
trehalose has been partially converted into hydrous crystalline
trehalose, i.e. dehydrated food products containing anhydrous
trehalose are obtainable by adding an excessive amount of anhydrous
trehalose to material food products in an amount of which exceeds
the moisture content in the food products; and that when the
dehydrated food products is injected into moistureproof packages
the moisture in the packages are entrapped by the anhydrous
trehalose for its conversion into hydrous crystalline trehalose,
whereby the relative humidity in the packages is decreased by a
large margin and the atmosphere in the packages is kept at a
relatively-high dryness. As a result, it was found that the
dehydrated food products obtained by the present invention are
prevented from bacterial contamination, as well as alteration or
deterioration such as hydrolysis, souring and browning, and because
of this the products with a satisfactory quality and taste are
stably retained for a relatively-long period of time.
In the preparation of dehydrated pharmaceuticals with a high
quality and a substantially-decreased moisture level, for example,
those in the form of massecuite and powder are readily prepared by
incorporating anhydrous trehalose into pharmaceuticals in liquid
form such as those containing lymphokines and antibiotics, as well
as those in paste form such as ginseng extract and snapping turtle
extract, to convert the anhydrous trehalose into hydrous
crystalline trehalose.
The preparations can provide a high quality and stable
dehydrated-pharmaceuticals because they do not require severe
conditions such as heat drying, and because the anhydrous trehalose
acts as a desiccant and stabilizer.
Conventional stabilizers such as water-soluble high
molecular-weight substances substantially do not waste energy for
their drying so that they can be favorably added to the dehydrated
pharmaceuticals to improve their qualities and stabilities.
The present invention can be advantageously practiced in the
preparations of solid pharmaceuticals by placing a prescribed
amount of anhydrous trehalose, for example, in a vial; adding to
the vial an aqueous solution containing a biologically active
substance such as a lymphokine or a hormone in an amount of which
is slightly-lower than the moisture content required for the
complete conversion of the anhydrous trehalose into hydrous
crystalline trehalose; and cap sealing the vial.
In this case, it was found that the anhydrous trehalose dehydrates
the aqueous solution containing a biologically active substance,
and dehumidifies the atmosphere in the vial.
It was also found that as a consequence the present invention
facilitates the preparation of dehydrated solid pharmaceuticals,
and still that the solid pharmaceuticals retain their high-quality
over a relatively-long period of time and readily dissolve in water
on use.
High quality and stable solid pharmaceuticals can be advantageously
prepared by mixing a prescribed amount of anhydrous trehalose while
a prescribed amount of an aqueous solution containing a
biologically active substance, placing the resultant powdery
product in a container, and sealing the container. If necessary,
the powdery product can be suitably formed into a granule or a
tablet in usual manner.
As described above, unlike conventional desiccants such as a silica
gel and a calcium oxide, the present desiccant using anhydrous
trehalose is edible, and, therefore it is assimilable and
alimentary in the body. It also acts as a stabilizer for
biologically active substances.
The present inventors studied on the preparation of anhydrous
trehalose, especially, the preparation of a powdery anhydrous
trehalose.
The anhydrous trehaloses suitably used in the invention are, for
example, anhydrous crystalline trehalose and anhydrous amorphous
trehalose.
In Journal of the Chemical Society, pp.3,489-3,490 (1965), G. Birch
reported a preparation of anhydrous crystalline trehalose by
crystallizing it in pyridine. The preparation is, however,
expensive because it requires an excessive amount of pyridine as a
solvent, and not satisfiable in view of the food sanitation.
In view of the prior art, the present inventors studied the
preparation of a powdery anhydrous crystalline trehalose and
established the preparation thereof, e.g. a preparation which
comprises providing an aqueous solution in which a commercially
available hydrous trehalose has been dissolved or providing an
aqueous trehalose solution prepared by extracting trehalose from
yeasts and purifying the resultant extract in accordance with a
method as described by M. Hayashibe and K. Aso in Hakko-Kyokai-shi,
Vol. 17, pp. 106-115 (1959); preparing such an aqueous solution
into a syrup with a relatively-high concentration and a moisture
content lower than about 10%, preferably, 2.0% or higher but lower
than 9.5%; keeping the syrup in the presence of a seed crystal at a
temperature of 50.degree.-160.degree. C. to crystallize anhydrous
crystalline trehalose; and pulverizing the resultant crystal.
The pulverizing methods usable in the invention are suitably chosen
from conventional methods such as a block pulverization, extruding
granulation, fluidized-bed granulation and spray-drying. The
anhydrous amorphous trehaloses usable in the invention can be
prepared from a commercially-available hydrous crystalline
trehalose or a concentrated solution of a high-purity trehalose
extracted and purified from yeasts.
In the case of using hydrous crystalline trehalose as a material
for anhydrous trehalose, the hydrous crystalline trehalose is
dissolved in water, dried in vacuo or at an atmospheric pressure
and at a temperature of about 100.degree.-160.degree. C., and
pulverized to obtain anhydrous trehalose. In the case of using an
aqueous solution of a high-purity trehalose as a material for
anhydrous trehalose, for example, an about 70-90% trehalose syrup
can be advantageously dried in vacuo or at an atmospheric pressure,
and pulverized into anhydrous trehalose. Alternatively, an about
60-85% trehalose syrup can be advantageously subjected to a
spray-drying such as a high-pressure nozzle method and a rotating
disk method to directly obtain a powdery anhydrous trehalose.
The powdery anhydrous trehaloses usable in the invention are
non-reducing saccharide powders in white having (i) a
satisfactorily high-quality and low-sweetness; (ii) a
relatively-low moisture content or substantially anhydrous,
usually, 3% or lower, preferably, 2% or lower on the Karl Fischer's
method; and (iii) a substantial free-flowing ability which may be
varied dependently on their particle size and shape.
The anhydrous trehalose as referred to in the invention includes
any substantially anhydrous trehalose as long as it absorbs
moisture and converts into hydrous crystalline trehalose to exert a
strong dehydrating activity. In order to augment the effect of
anhydrous trehalose as a desiccant, trehalose can be formulated to
coexist in a powdery anhydrous amorphous trehalose the lowest
possible amount of hydrous crystalline trehalose as a seed crystal,
usually, in an amount lower than 5%, preferably, lower than one %,
whereby the conversion rate of anhydrous trehalose into hydrous
crystalline trehalose is improved.
It was found that the powdery anhydrous trehalose thus obtained
acts as a desiccant with a strong dehydrating activity against
hydrous matters in a manner such that it entraps and fixes the
moisture contained in hydrous matters such as food products,
pharmaceuticals, cosmetics and industrial chemicals when
incorporated into the hydrous matters.
The present desiccant can be advantageously used to dehumidify and
dry the atmosphere in a moistureproof package, as well as to
prepare a high-quality dehydrated product in massecuite or powder
form from a hydrous matter which is susceptible to alteration and
deterioration during heat drying- or vacuum drying-step, as well as
from those which are substantially difficult to dry.
The present desiccant can be suitably used to dehumidify and dry
hydrous matters. For example, it can be used to prevent
"ajitsuke-nori" and cookies from absorbing moisture, or
advantageously incorporated into powdery products which readily
absorb moisture to form solid products, for example, ready-mixed
powders such as those of purine and hot cake; powdery seasonings
such as salt, sugar, powdered soy sauce, powdered "miso" (soybean
paste), powdered "sushi-su" (a vinegar), powdered "dashi-no-moto",
powdery mixed seasoning, powdered paprika, powdered garlic,
powdered cinnamon, powdered nutmeg, powdered pepper and powdered
sage; and other powdery products such as powdered yeast extract,
powered milk, powdered yogurt, powdered cheese, powdered juice,
powdered herb, powdered vitamin, granulated soup, granulated
bouillon, fish flour, blood meal, bone meal, powdered agent of
lactic acid bacteria, powdered enzyme and granulated digestive;
followed by placing the resultant dehydrated product into a
package, whereby (i) the relative humidity within the package is
decreased, and (ii) the resultant product is prevented from
solidification and adhesion to the package, and satisfactorily
retains its quality for a relatively-long period of time.
The desiccant according to the present invention can be suitably
used to dehydrate hydrous matters such as organs, tissues, cells,
homogenates, extracts and components derived from animals, plants
and microorganisms, as well as preparations therefrom.
When a hydrous matter is a food product, or its materials or
intermediates exist in liquid or paste form, a stable and tasty
dehydrated food product can be readily prepared according to the
invention. Examples of such a hydrous matter are agricultural
products such as fresh fruit, juice, vegetable extract, soybean
milk, sesame paste, nut paste, "nama-an" (unsweetened bean jam),
gelatinized starch paste and wheat flour; marine products such as
sea urchin paste, oyster extract and sardine paste; poultry and
livestock products such as fresh egg, lecithin, milk, whey, fresh
cream, yogurt, butter and cheese; hydrous seasonings such as maple
syrup, honey, "miso" (soybean paste), soy sauce, mayonnaise,
dressing, bonito extract, meat extract, tangle extract, chicken
extract, beef extract, yeast extract, mushroom extract, licorice
extract, stevia extract, enzymatically processed product thereof
and seasoning liquid for pickles; liquors such as Japanese sake,
wine, brandy, whisky and medical liqueur; soft drinks such as a
tea, green tea and coffee; hydrous spices such as those extracted
from peppermint, "wasabi" (Japanese horseradish), garlic, mustard,
"sansho" (Japanese pepper tree), cinnamon, sage, laurel, pepper and
citrus fruit; hydrous coloring agents such as those extracted from
madder, annatto (Bixa oreliana), turmeric, paprika, red beet,
safflower, cape jasmine, saffron and extract from microorganism of
the genus Monascus; hydrous emulsifiers such as a fatty acid sugar
ester, glycerine, fatty acid ester and sorbitan fatty acid ester;
and preservatives in liquid or paste form such as a smoke solution
and a fermented solution.
The dehydrated products obtained in this way, for example, a
powdered agricultural- or poultry-product, powdered oil and fat,
powdery flavor and powdery coloring agent can be conveniently used,
for example, as a natural bulk flavor excellent in taste and
flavor, in various food products, for example, seasonings such as a
mayonnaise and soup stock; confectioneries such as a hard candy and
cake; and materials for food products such as a hot cake mix and
instant juice.
When a hydrous matter is a pharmaceutical, or its material or
intermediate, it can be readily prepared into a stable and
highly-active pharmaceutical according to the present invention
without inactivating the effective ingredients. Examples of such a
hydrous matter are a solution containing lymphokine such as an
.alpha.-, .beta.- .gamma.-interferon, tumor necrosis factor-.alpha.
(TNF-.alpha.), tumor necrosis factor-.beta. (TNF-.beta.),
macrophage migration inhibitory factor, colony-stimulating factor,
transfer factor and interleukin 2; a solution containing hormone
such as insulin, growth hormone, prolactin, erythropoietin and
follicle-stimulating hormone; a solution containing a biological
preparation such as BCG vaccine, Japanese encephalitis vaccine,
measles vaccine, live polio vaccine, smallpox vaccine, tetanus
toxoid, Trimeresurus antitoxin and human immunoglobulin; a solution
containing an antibiotic such as penicillin, erythromycin,
chloramphenicol, tetracycline, streptomycin and kanamycin sulfate;
a solution containing a vitamin such as thiamine, riboflavin,
L-ascorbic acid, liver oil, carotenoid, ergosterol and tocopherol;
a solution containing an enzyme such as lipase, elastase,
urokinase, protease, .beta.-amylase, isoamylase, glucanase and
lactase; an extract such as ginseng extract, snapping turtle
extract, chlorella extract, aloe extract and propolls extract; a
paste of cell or minute infectious agent such as those of virus,
lactic acid bacterium and yeast; and a liquid or paste such as
royal jelly.
In order to dehydrate hydrous matters such as a cosmetic and its
materials or intermediates, a high-quality cosmetic can be readily
prepared by dehydrating a hydrous matter such as a fresh egg,
lecithin, fresh cream, honey, licorice extract, flavor, coloring
agent or an enzyme similarly as in the cases of food products and
pharmaceuticals.
The cosmetic thus obtained can be advantageously used as a skin- or
hair-treatment, as well as a hair restorer. When a dehydrated
product is of an enzyme, it can be advantageously used as a
therapeutic agent, digestive and enzymatic detergent, as well as a
catalyst for the preparations of food products, pharmaceuticals and
industrial materials.
Any conventional method such as mixing, kneading, dissolving,
permeating, soaking, sprinkling, coating, spraying, crystallizing
and injecting can be suitably employed as a method to incorporate
anhydrous trehalose into hydrous matters before the completion of
the processings of the objective dehydrated products.
Although the amount of anhydrous trehalose to be incorporated into
a hydrous matter is varied depending on the moisture content and
property of the hydrous matter, it is generally 0.01-200 parts by
weight, desirably, 0.01-50 parts by weight to one part by weight of
the hydrous matter. If necessary, the anhydrous trehalose may be
incorporated into a hydrous matter after the hydrous matter has
been partially dehydrated or concentrated by conventional method.
In such a case, in order to improve the quality of the objective
dehydrated-products such as food products, pharmaceuticals and
cosmetics, an adequate flavor-imparting agent, coloring agent,
taste-imparting agent, stabilizer and/or filler can be suitably
used in combination with the anhydrous trehalose.
Examples of such a stabilizer are water-soluble polymers which have
been hardly deemed to be dehydrated, and not limited to a
relatively-low molecular-weight compound such as an antioxidant
because the present method for dehydration employs anhydrous
trehalose with a strong dehydrating activity. Examples of such a
water-soluble polymer suitably used as a stabilizer in the
invention are soluble starch, dextrin, pullulan, elsinan, dextran,
xanthan gum, gum arabic, locust bean gum, guar gum, tragacanth gum,
carboxymethyl starch, hydroxyethyl cellulose, pectin, agar,
gelatin, albumin and casein.
When such a water-soluble polymer is used as a stabilizer, a
dehydrated food product containing microcrystals of hydrous
crystalline trehalose can be prepared by first dissolving a
water-soluble polymer to homogeneity in a hydrous matter in liquid
or paste form, then incorporating anhydrous trehalose to
homogeneity into the resultant solution by a method such as mixing
or kneading.
The product thus obtained retains the flavor and effective
components of the material hydrous matter because the flavor and
effective components are coated with a membrane of the
above-mentioned water-soluble polymer, or enclosed in a
microcapsule surrounded by the membrane together with the
microcrystals of hydrous crystalline trehalose. Because of this,
the flavor and effective components are prevented from
volatilization and deterioration, and stably retained in the
microcapsule. If necessary, cyclodextrins, which form an inclusion
complex with the flavor and the effective components, can be
suitably used as a water-soluble polymer in combination with the
anhydrous trehalose.
The cyclodextrins usable in the invention are not restricted to
those with the highest possible purity, and may be those with a
relatively-low purity which can be hardly dried and pulverized. For
example, syrups of a partial starch hydrolyzate containing
cyclodextrins together with a large amount of maltodextrins can be
favorably used. The methods to prepare dehydrated products usable
in the present invention, especially, those to prepare powdery
products are varied. For example, dehydrated products or powdery
products can be prepared by a method comprising homogeneously
mixing a hydrous matter having a relatively-high moisture content
such as food products, pharmaceuticals, cosmetics and their
materials or intermediates with anhydrous trehalose to obtain a
mixture having a moisture content of about 40% or lower,
preferably, 10-30%; placing the mixture in a container; allowing
the container to stand at about 10.degree.-50.degree. C., e.g. at
an ambient temperature, for about 0.1-5 days to solidify the
mixture while the anhydrous trehalose is permitted to convert to
hydrous crystalline trehalose; and cutting or pulverizing the
resultant solid product. If necessary, a drying step and/or a
classification step may be added to the cutting or pulverizing
step. Furthermore, powdery products can be directly obtained by
subjecting a mixture of a hydrous matter and anhydrous trehalose
onto a spray-drying, etc.
Such a powdery product can be also prepared by a method (I)
comprising spraying a prescribed amount of a hydrous matter in
liquid or paste form to anhydrous trehalose in a state of flux,
granulating the resultant mixture while the hydrous matter is in
contact with the anhydrous trehalose, and, if necessary further
ageing the resultant granule at a temperature of about
30.degree.-60.degree. C. for about 0.1-10 hours to convert the
anhydrous trehalose into hydrous crystalline trehalose; and a
method (II) comprising mixing or kneading anhydrous trehalose with
a hydrous matter in liquid or paste form, and spraying the
resultant mixture instantly or after the initiation of the
conversion of the anhydrous trehalose into hydrous crystalline
trehalose. If necessary, the powdery product thus obtained may be
further aged similarly as in method (I) to convert the anhydrous
trehalose into hydrous crystalline trehalose. Methods (I) and (II)
can be suitably employed in the invention as a mass production of a
powdery dehydrated-product.
In the case of such a spray-drying, it can be advantageously
practiced to coexist with anhydrous trehalose the lowest possible
level of hydrous crystalline trehalose as a seed crystal in order
to promote the conversion of the anhydrous trehalose into hydrous
crystalline trehalose, whereby the ageing period of time is
satisfactorily shortened or the ageing step can be even eliminated.
The powdery dehydrated-product thus obtained can be used alone,
and, if necessary it can be formed into a product in liquid or
paste form in combination with a filler, excipient, binder and/or
stabilizer, and freely formed into a granule, tablet, capsule, rod,
plate or cube.
Sugar-coating products can be advantageously prepared by coating a
core or a center, for example, a food product such as a peanut,
almond or candy, or a pharmaceutical intermediate in the form of a
granule or a crude tablet, with an aqueous solution containing
about 60-90% of anhydrous trehalose, preferably, a solution
containing anhydrous trehalose together with an adequate amount of
a binder such as a water-soluble polymer to crystallize hydrous
crystalline trehalose on the core.
Generally, starch requires a relatively-large amount of moisture in
order to Sweiland gelantinize. For this reason, gelatinized starch
is highly susceptible to bacterial contamination. Anhydrous
trehalose can be favorably used as a desiccant for dehydrating such
a gelatinized starch. For example, "gyuhi" (a gelatinized starch in
paste form) is prevented from bacterial contamination by
incorporating anhydrous trehalose into the gelatinized starch to
convert the anhydrous trehalose into hydrous crystalline trehalose,
whereby the moisture in the gelatinized starch is substantially
decreased.
Anhydrous trehalose readily disperses homogeneously into
gelatinized starch and acts as a retrogradation-preventing agent,
and because of this anhydrous trehalose satisfactorily prolongs the
shelf life of a variety of processed food products containing
gelatinized starch.
Anhydrous trehalose can be used as a food preservative, stabilizer
and quality-improving agent in hydrous food products having a
relatively-high moisture content such as a peeled banana, orange,
sliced steamed-potato, opened horse-mackerel, Pacific saury, raw
noodle, boiled noodle and bean-jam cake by sprinkling anhydrous
crystalline trehalose as an anhydrous trehalose over the surface of
the hydrous food products to convert the anhydrous crystalline
trehalose into hydrous crystalline trehalose, whereby the moisture
on the surface of the hydrous food products is substantially
decreased, and their qualities and shelf lives are satisfactorily
improved and prolonged. In this case, when a more prolonged shelf
life is required, the anhydrous crystalline trehalose can be
suitably used in combination with lactic acid, citric acid and/or
ethanol; and, if necessary the resultant dehydrated products may be
subjected to a vacuum package, a gas flush package or a cold
storage.
Anhydrous trehalose has a relatively-high affinity for alcohols.
This property renders anhydrous trehalose useful as a desiccant to
remove moisture contained in alcohols such as methanol, ethanol,
butanol, propylene glycol, glycerin and polyethylene glycol, as
well as in alcohol-soluble substances.
For example, dehydrated liquors in massecuite or powdery form,
which retain the effective ingredients and flavors of liquors, can
be prepared by dehydrating with anhydrous trehalose liquors such as
"sake" (Japanese rice wine), "shochu" (low-class distilled
spirits), wine, brandy, whisky and vodka. The powdery
dehydrated-liquors thus obtained can be used in confectioneries and
ready-mix powders, or used by dissolving them in water prior to
their use.
In this case, anhydrous trehalose can exert a satisfactory effect
as a desiccant and stabilizer, as well as a mild sweetener, filler
and adequate viscosity-imparting agent.
Effective elements such as iodine can be stably retained by mixing
an alcohol-soluble substance such as iodine with anhydrous
trehalose, and mixing the resultant mixture with an aqueous
solution containing a water-soluble high molecular-weight substance
to convert the anhydrous trehalose into hydrous crystalline
trehalose. Thus, an ointment in massecuite form having an adequate
viscosity, extensibility and adhesiveness can be favorably
prepared.
Dehydrated products, for example, powdery food products such as
those of oils and fats, seasonings, flavors and color-imparting
agents; powdery cosmetics; and powdery pharmaceuticals such as
those of vitamins and hormones can be favorably prepared by
incorporating anhydrous trehalose into their material products to
convert it into hydrous crystalline trehalose while impregnating or
mixing the anhydrous trehalose with a latex, an emulsified product
or a hydrous oil-soluble substance.
In this case, anhydrous trehalose acts as a desiccant, and the
converted hydrous crystalline trehalose acts as a stabilizer,
preservative, filler and carrier.
Anhydrous trehalose can be suitably used in food products
containing oil-soluble substances such as a chocolate and cream
filling which are apt to be readily damaged by moisture. In this
case, anhydrous trehalose is used as a desiccant, as well as an
agent for improving the processibility, flavor and meltability in
the mouth. The dehydrated food products thus obtained has a
relatively-long shelf-life.
As described above, the present invention was made based on the
findings that anhydrous trehalose strongly dehydrates hydrous
matters, and that the resultant dehydrated products have a
satisfiable stability. By using the anhydrous trehalose as a
desiccant, high-quality food products and cosmetics with a
decreased moisture-content can be favorably prepared without
deteriorating or losing their flavors and tastes; and high-quality
pharmaceuticals and cosmetics with a decreased moisture-content can
be favorably prepared without decomposing or losing their effective
ingredients or activities.
In addition to the aforementioned specific properties, anhydrous
trehalose as a natural sweetener is readily assimilated and
utilized by the body without fear of causing cariogenicity and
increasing the blood cholesterol-level, and has substantially the
same level of nutritive value as maltooligosaccharides. Anhydrous
trehalose has a mild sweetness, body-imparting ability,
gloss-imparting ability, viscosity-imparting ability and
moisture-retaining ability, and these render it advantageously
useful in food products, pharmaceuticals and cosmetics.
The followings are illustrative of additional uses of anhydrous
trehalose:
Anhydrous trehalose can be used as a seasoning with a strong
dehydrating activity. If necessary, it can be used together with
one or more other sweeteners, for example, powdered syrup, glucose,
isomerized sugar, sucrose, maltose, honey, maple sugar, sorbitol,
maltitol, dihydrocharcone, stevioside, .alpha.-glycosyl stevioside,
sweet substance derived from Momordica grosvenori Swingle,
glycyrrhizin, thaumatin, L-aspartyl L-phenylalanine methyl ester,
saccharin, glycine and alanine; and/or a filler such as dextrin,
starch and lactose.
Anhydrous trehalose, a non-reducing saccharide, has features: (i)
it has the inherent mild sweetness of trehalose; (ii) it well
harmonizes with other materials having sour-, acid-, salty-,
bitter-, astringent- and delicious-tastes, and (iii) it is highly
acid- and heat-resistant. Thus, anhydrous trehalose can be
favorably used in food products in general as a desiccant, as well
as a sweetener, taste-improving agent and quality-improving
agent.
Anhydrous trehalose is used as a desiccant, sweetener,
taste-improving agent and quality-improving agent in seasonings
such as soy sauce, powdered soy sauce, "miso", "funmatsu-miso" (a
powdered miso), "moromi" (a refined sake), "hishio" (a refined soy
sauce), "furikake" (a seasoned fish meal), mayonnaise, dressing,
vinegar, "sanbai-zu" (a sauce of sugar, soy sauce and vinegar),
"funmatsu-sushi-su" (powdered vinegar for sushi), "chuka-no-moto"
(an instant mix for Chinese dish), "tentsuyu" (a sauce for Japanese
deep-fat fried food), "mentsuyu" (a sauce for Japanese vermicelli),
sauce, catsup, "yakiniku-no-tare" (a sauce for Japanese grilled
meat), curry roux, instant stew mix, instant soup mix,
"dashi-no-moto" (an instant stock mix), mixed seasoning, "mirin" (a
sweet sake), "shin-mirin" (a synthetic mirin), table sugar and
coffee sugar.
Also, anhydrous trehalose can be freely used for dehydrating
"wagashi" (Japanese cakes) such as "senbei" (a rice cracker),
"arare-mochi" (a rice-cake cube), "okoshi" (a millet-and-rice
cake), "gyuhi" (a rice paste), "mochi" (a rice paste), "manju" (a
bun with a bean-jam), "uiro" (a sweet rice jelly), "an" (a bean
jam), "Uokan" (a sweet jelly of beans), "mizu-Uokan" (a soft
adzuki-bean jelly), "kingUoku" (a kind of yokan), jelly, pao de
Castella and "amedama" (a Japanese toffee); confectioneries such as
bakery products such as bun, biscuit, cracker, cookie, pie,
pudding, butter cream, custard cream, cream puff, waffle, sponge
cake, doughnut, chocolate, chewing gum, caramel and candy; frozen
desserts such as ice cream and sherbet; syrups such as
"kajitsu-no-syrup-zuke" (a preserved fruit) and "korimitsu" (a
sugar syrup for shaved ice); pastes such as flour paste, peanut
paste and fruit paste; processed fruits and vegetables such as jam,
marmalade, "syrup-zuke" (fruit pickles) and "toka" (conserves);
pickles and pickled products such as "fukujin-zuke" (red colored
radish pickles), "bettara-zuke" (a kind of whole fresh radish
pickles), "senmai-zuke" (a kind of sliced fresh radish pickles) and
"rakkyo-zuke" (pickled shallots); premixes for pickles and pickled
products such as "takuan-zuke-no-moto" (a premix for pickled
radish) and "hakusai-zuke-no-moto" (a premix for fresh white rape
pickles); meat products such as ham and sausage; fish meat products
such as fish ham, fish sausage, "kamaboko" (a steamed fish paste),
"chikuwa" (a kind of fish paste) and "tenpura" (a Japanese deep-fat
fried fish paste); "chinmi" (relish) such as "uni-no-shiokara"
(salted guts of sea urchin), "ika-no-shiokara" (salted guts of
squid), "su-konbu" (processed tangle), "saki-surume" (dried squid
strips), "fugu-no-mirin-boshi" (a dried mirin-seasoned swellfish),
and mashed and seasoned food of cod, sea bream and shrimp;
"tsukudani" (foods boiled down in soy sauce) such as those of
laver, edible wild plants, dried squid, fish and shellfish; daily
dishes such as "nimame" (cooked beans), potato salad and
"konbu-maki" (a tangle roll); milk products; canned and bottled
products such as those of meat, fish meat, fruit and vegetable;
alcoholic beverages such as synthetic sake, "zozyo-shu", fruit wine
and liquors; soft drinks such as coffee, cocoa, juice, carbonated
beverage, sour milk beverage and beverage containing a lactic acid
bacterium; instant food products such as instant pudding mix,
instant hot cake mix, juice power, instant coffee,
"sokuseki-shiruco" (an instant mix of adzuki-bean soup with rice
cake) and instant soup mix; as well as for sweetening the
aforementioned food products and improving their tastes and
qualities.
The following experiments explain the present invention in
detail:
EXPERIMENT 1
Comparison of Dehydrating Activities of Non-reducing Saccharides
and Stabilities of Dehydrated Products Prepared Therewith
Non-reducing saccharides used in this experiment were sucrose,
anhydrous crystalline trehalose, anhydrous amorphous trehalose,
hydrous crystalline trehalose, anhydrous amorphous neotrehalose,
hydrous crystalline neotrehalose, hydrous amorphous erlose, hydrous
crystalline erlose, anhydrous amorphous raffinose, hydrous
crystalline raffinose, anhydrous amorphous melezitose and hydrous
crystalline melezitose. The sucrose, hydrous crystalline trehalose,
hydrous crystalline erlose, hydrous crystalline raffinose and
hydrous crystalline melezitose were the grades of commercially
available reagents. The anhydrous crystalline trehalose and
anhydrous amorphous trehalose were respectively prepared by the
methods in Examples for reference 1 and 3. The anhydrous
crystalline neotrehalose was prepared by the method in Experiment 2
as disclosed in Japanese Patent Laid-Open No. 179,490/92. The
anhydrous amorphous neotrehalose, anhydrous amorphous erlose,
anhydrous amorphous raffinose and anhydrous amorphous melezitose
were respectively prepared by dissolving each of them in water, and
drying the resultant solution in vacuo at an ambient
temperature.
The non-reducing saccharides were studied on their dehydrating
activities. A mixture, obtained by mixing 2 parts by weight of a
plain yogurt with 8 parts by weight of one of the non-reducing
saccharides, was placed in a container and allowed to stand at
25.degree. C. overnight, followed by observing the macroscopic
change of the resultant mixture. The dehydrating activities of the
non-reducing saccharides were graded into 3 ranks, i.e. "High"
meaning that it formed a complete solidification; "Low", that it
formed an incomplete solidification; and "Non", that it showed no
substantial change.
The completely solidified-products were studied on their
stabilities: Each product was pulverized by a cutter to obtain a
powdery product which was then granulated to give a granular size
of about 100-150.mu.m. Thirty g aliquots of the granules were
placed in plastic petri-dishes, and allowed to stand at 37.degree.
C. and a relative humidity of 70% for 2 weeks, followed by
comparing the degree of color of the resultant product. The degree
of color was defined as a difference between the absorbances at the
wave lengths of 420nm and 720nm determined in a 10-cm cell with a
supernatant prepared from a 30 w/v suspension of each solidified
product. The stabilities of the dehydrated products were graded
into the following ranks: "Superior" meaning that it showed a
degree lower than 0.1; "Middle", that it showed a degree of 0.1 or
higher but lower than 0.2; and "Inferior", that it showed a degree
of 0.2 or higher.
The results were as shown in Table 1.
TABLE 1
__________________________________________________________________________
Stability of Dehydrating dehydrated Saccharide Macroscopic Change
activity product Judgement
__________________________________________________________________________
Sucrose Unchanged Non -- Control Anhydrous crystalline Completely
solidified High Superior Present invention trehalose Anhydrous
amorphous Completely solidified High Superior Present invention
trehalose Hydrous crystalline Unchanged Non -- Control trehalose
Anhydrous amorphous Incompletely solidified Low -- Control
neotrehalose Hydrous crystalline Unchanged Non -- Control
neotrehalose Anhydrous amorphous Completely solidified High
Inferior Control erlose Hydrous crystalline Unchanged Non --
Control erlose Anhydrous amorphous Completely solidified High
Inferior Control raffinose Hydrous crystalline Unchanged Non --
Control raffinose Anhydrous amorphous Incompletely solidified Low
-- Control melezitose Hydrous crystalline Unchanged Non -- Control
melezitose
__________________________________________________________________________
Note: In the Table, the symbol "--" means that the stability test
of a mixture could not be done because of its incomplete
solidification.
As evident from the results in Table 1, it was revealed that the
anhydrous crystalline trehalose and the anhydrous amorphous
trehalose had a strong dehydrating activity, and the dehydrated
products prepared therewith had a satisfactorily-high stability.
Thus, anhydrous trehalose can be advantageously used as a
desiccant.
EXPERIMENT 2
Dehydration by Anhydrous Trehalose
The dehydrating activities of archydious crystalline trehalose and
anhydrous amorphous trehalose as an anhydrous trehalose were
studied, i.e. the levels of their dehydrating activities and their
dehydrating moisture-levels were studied in detail. As a control,
hydrous crystalline trehalose was used. The procedure of this
experiment was as follows: Each anhydrous trehalose obtained by the
method in Experiment 1 was prepared into a powdery product having a
grain size of about 100-150.mu.m. One g of the powdery product was
placed in a plastic petri-dish having a diameter of 5cm, and
allowed to stand at 25.degree. C. and a relative humidity of 70%,
followed by measuring the moisture content (%) of the resultant
product at a prescribed time-interval. The results were as shown in
Table 2.
TABLE 2 ______________________________________ Time Trehalose 0 4 8
24 72 ______________________________________ Anhydrous crystalline
0.32 6.42 8.35 9.65 9.80 trehalose Anhydrous amorphous 0.83 8.20
9.57 9.80 9.80 trehalose Hydrous crystalline 9.57 9.60 9.62 9.64
9.70 trehalose ______________________________________
As evident from the results in Table 2, it was revealed that the
anhydrous trehaloses exerted a strong dehydrating activity, i.e.
they entrapped moisture in the atmosphere in an amount of about 10%
by weight of the anhydrous trehaloses, on a dry solid basis
(d.s.b.). The anhydrous trehaloses were studied on their x-ray
powder diffraction figures at a prescribed time-interval to reveal
that they entrapped moisture and converted into hydrous crystalline
trehaloses, and that the resultant products equilibrated and
stabilized when absorbed about 10% moisture. An x-ray diffraction
figure of hydrous crystalline trehalose was as shown in FIG. 1.
Similarly as above, the anhydrous trehaloses were allowed to stand
at 25.degree. C. and a relative humidity of about 90%, followed by
measuring the moisture contents (%) of the resultant products at a
prescribed time-interval. Similarly as in the above, the anhydrous
trehaloses were converted into hydrous crystalline trehalose and
equilibrated when absorbed about 10% moisture. In this case, the
resultant products retained their powdery forms and no phenomenon
such as sticking and flowing was observed.
Based on these properties, it was revealed that anhydrous trehalose
can be advantageously used as a desiccant for food products,
pharmaceuticals, cosmetics and their materials or
intermediates.
EXPERIMENT 3
Comparison of Dynamics of Anhydrous Trehalose and Hydrous
Crystalline Trehalose Against Gelatinized Starch
Four parts by weight of powdery glutinous rice was suspended in 6
parts by weight of water, and the suspension was poured onto a wet
close covered over the inside surface of a wooden container, and
steamed up at 105.degree. C. for 10 minutes to obtain a gelatinized
starch. To the gelatinized starch was added 7 parts by weight of
hydrous crystalline trehalose or anhydrous crystalline trehalose
prepared by the method in Example for reference 1, and the
resultant was mixed by a mixer until it showed homogeneity.
Thereafter, the resultant mixture was sufficiently kneaded with 2
parts by weight of a starch hydrolyzate, formed, and mildly dried
with a 40.degree. C. hot-air for 2 hours to obtain "gyuhi" (a rice
paste).
When the product prepared with anhydrous- or hydrous-crystalline
trehalose was allowed to stand at 25.degree. C. without packaging,
a colony of a black mold was observed in the product with hydrous
crystalline trehalose after 15 days of its processing, while no
bacterial contamination was observed in the product with anhydrous
crystalline trehalose even after 30 days of its processing.
The product with anhydrous crystalline trehalose after 30 days of
its processing was cut into sections, and the sections were
observed to find that the texture near the surface of the product
exhibited only a slight solidification and had a crystalline
trehalose, while the inner texture exhibited the same level of
satisfiable semi-transparency, gloss and viscosity as the product
immediately after its processing. An x-ray diffraction figure
revealed that the crystalline trehalose was hydrous crystalline
trehalose which had been converted from anhydrous crystalline
trehalose.
As a result, it was revealed that anhydrous trehalose acts as a
desiccant for gelatinized starch and prevents bacterial
contamination, as well as the retrogradation of gelatinized starch.
Anhydrous trehalose having these satisfiable properties can be
favorably used in a variety of products prepared with gelatinized
starch such as "gyuhi" and flour paste.
The preparation of powdery anhydrous trehalose according to the
invention are described in the following Examples for
reference:
Example for Reference 1
Hydrous crystalline trehalose was dissolved by heating in a small
amount of water, and the resultant aqueous solution was placed in a
vessel and boiled down in vacuo to obtain a syrup with a moisture
content of 5.0%. The syrup was transferred to a crystallizer, mixed
with one % by weight of anhydrous crystalline trehalose as a seed
crystal against the syrup, d.s.b., and allowed to crystallize
trehalose at 120.degree. C. for 5 minutes under stirring
conditions. The resultant massecuite was transferred to an aluminum
container and aged at 100.degree. C. for 6 hours to form a
block.
The resultant block was pulverized by a cutter into a powdery
product which was then subjected to a fluidized-bed drying to
obtain an anhydrous crystalline trehalose with a moisture content
of 0.32% in the yield of about 87% against the material hydrous
crystalline trehalose, d.s.b. The powder x-ray diffraction figure
of the anhydrous crystalline trehalose was as shown in FIG. 2.
The product can be favorably used as a desiccant for hydrous
matters such as food products, pharmaceuticals, cosmetics and their
materials or intermediates, as well as a white powdery sweetener
with a mild sweetness.
Example for Reference 2
An aqueous solution of a high-purity trehalose was placed in a
vessel and boiled down in vacuo to obtain a syrup with a moisture
content of 4.0%, which was then mixed with 5% by weight of
anhydrous crystalline trehalose as a seed crystal against the
syrup, d.s.b., and allowed to crystallize trehalose at 95.degree.
C. under stirring conditions. The resultant crystal was granulated
by a granulator, aged, dried and pulverized by a pulverizer to
obtain a powdery anhydrous crystalline trehalose with a moisture
content of 0.53% in the yield of about 95% against the material
trehalose, d.s.b.
Similarly as the powdery anhydrous crystalline trehalose obtained
by the method in Example for reference 1, the product can be
favorably used as a desiccant, as well as a sweetener for a variety
of hydrous matters.
Example for Reference 3
Hydrous crystalline trehalose was completely dissolved in water at
an ambient temperature, and the resultant aqueous solution was
dried in vacuo at 60.degree. C. for 24 hours. The resultant
dehydrated product was pulverized by a pulverizer to obtain an
anhydrous amorphous trehalose with a moisture content of 0.83% in
the yield of about 89% against the material hydrous crystalline
trehalose, d.s.b. The powder x-ray diffraction figure of the
anhydrous amorphous trehalose was as shown in FIG. 3.
Similarly as the powdery anhydrous crystalline trehalose obtained
by the method in Example for reference 1, the product can be
favorably used as a sweetener, as well as a desiccant for a variety
of hydrous matters.
The examples and advantageous effects of the present invention are
disclosed hereinafter:
EXAMPLE 1
Desiccant
Twenty g aliquots of an anhydrous crystalline trehalose, obtained
by the method in Example for reference 1, were injected into
moisture-permeable small paper-bags to obtain a desiccant. The
product can be favorably used as a desiccant to dehydrate the
atmosphere in a moistureproof package injected with a dehydrated
food product such as a cookie or a toasted and seasoned laver.
Dehydrated- and oily-food products can be stably stored by using
the product in combination with an oxygen scavenger.
EXAMPLE 2
"Soboro-gyuhi" (a Starch Paste)
Four parts by weight of a powdery glutinous rice was suspended in 6
parts by weight of water, and the resultant suspension was poured
onto a wet cloth covered over the inside surface of a wooden
container, steamed at 100.degree. C. for 20 minutes, mixed with one
part by weight of sucrose and 7 parts by weight of an anhydrous
crystalline trehalose obtained by the method in Example for
reference 1, and further sufficiently mixed with 2 parts by weight
of a starch hydrolyzate. The resultant mixture was formed and
allowed to stand at an ambient temperature for 16 hours to convert
the anhydrous trehalose into hydrous crystalline trehalose on the
surface of the resultant product, which was then mildly rolled to
form cracks on its surface to obtain the captioned product. The
product had a satisfiable flavor and retained its high quality for
a relatively-long period of time without substantial bacterial
contamination.
EXAMPLE 3
Confectionery Made of Sweet Potato
A sweet potato was sliced into thin pieces about 1-cm thick, and
the pieces were steamed, cooled at ambient temperature, and
dehydrated by dusting over them with an anhydrous crystalline
trehalose prepared by the method in Example for reference 1 to
convert the anhydrous crystalline trehalose into hydrous
crystalline trehalose. Thus, the captioned product, having hydrous
crystalline trehalose adhered on its surface, was prepared. The
product had a satisfactory flavor and stability.
EXAMPLE 4
Brandy Powder
Ten parts by weight of pullulan was dissolved in 2 parts by weight
of a brandy, and the resultant solution was mixed with 8 parts by
weight of an anhydrous crystalline trehalose obtained by the method
in Example for reference 2. The resultant mixture was transferred
to a container, and allowed to stand for 2 days to form a block
while allowing the anhydrous crystalline trehalose to convert to
hydrous crystalline trehalose. The block was pulverized by a
pulverizer and classified to obtain a brandy powder with a
satisfactory flavor. The product is a flavored powder having an
adequate sweetness and a sufficient brandy-flavor, and you can
enjoy it in your mouth. The product can be favorably used as a
flavor-imparting agent for tea, as well as a material for
confectioneries such as a premix powder and candy. The product can
be favorably formed into a granule or a tablet by a granulator or a
tabletting machine.
EXAMPLE 5
"Miso" Powder
Two parts by weight of "akamiso" (a kind of miso) was mixed with 5
parts by weight of an anhydrous crystalline trehalose prepared by
the method in Example for reference 2, and the resultant mixture
was poured onto a metal plate provided with semispheric
depressions, allowed to stand at an ambient temperature overnight
to solidify the mixture in the depressions. The solidified products
in the depressions were removed therefrom to obtain solid products,
about 4 g each, which were then subjected to a pulverizer to obtain
the captioned product. The product can be favorably used as a
seasoning in an instant noodle and instant soup. When the product
is formed into a solid product, it can be used as a solid seasoning
or a miso confectionery.
EXAMPLE 6
Soy Sauce Powder
A mixture, consisting of 0.02 parts by weight of a commercially
available hydrous crystalline trehalose and 4 parts by weight of an
anhydrous crystalline trehalose prepared by the method in Example
for reference 3, was sprayed with "usukuchi-shoyu" (a less-colored
soy sauce) to give the final content of one part by weight while
the mixture was moving on a conveyer belt, transferred to an ageing
tower, and allowed to stand at 30.degree. C. overnight to covert
the anhydrous trehalose into hydrous crystalline trehalose. Thus,
the captioned product was obtained. The product can be favorably
used as a seasoning for an instant noodle or an instant soup.
EXAMPLE 7
Egg-yolk Powder
An egg yolk prepared from a fresh egg was sterilized at
60.degree.-64.degree. C. by a plate-type heat sterilizer to obtain
a liquid egg yolk. To one part by weight of the liquid egg yolk was
added 4 parts by weight of an anhydrous crystalline trehalose
prepared by the method in Example for reference 1, and, similarly
as in Example 4 the resultant mixture was formed into a block which
was then pulverized into an egg-yolk powder. The product can be
favorably used as a material for confectioneries such as premix
powders, ice products and emulsifiers, as well as baby foods and
therapeutic nutrients such as intubation foods and orally
administrable fluid-foods. The product can be favorably used as a
skin refiner and a hair restorer.
EXAMPLE 8
Yogurt Powder
Two parts by weight of plain yogurt was mixed with 8 parts by
weight of an anhydrous crystalline trehalose prepared by the method
in Example for reference 1, and, similarly as in Example 4 the
resultant mixture was formed into a block which was then pulverized
into a yogurt powder. The product had a satisfactory flavor and
stably retained lactic acid bacteria alive for a relatively-long
period of time. The product can be favorably used as a material for
confectioneries such as premix powders, ice products, emulsifiers
and baby foods, as well as therapeutic nutrients such as intubation
foods and orally-administrable fluidfoods. The product can be
favorably incorporated into margarine, whipped cream, spread,
cheese cake and jelly to obtain a product having a yogurt-like
flavor. The product can be formed by a granulator or a tabletting
machine into a preparation of lactic acid bacteria which can be
favorably used as an agent for intestinal disorder.
EXAMPLE 9
Hot Cake Mix
A hot cake mix was obtained by mixing 200 parts by weight of a
wheat flour with 60 parts by weight of an egg yolk powder prepared
by the method in Example 7, 25 parts by weight of butter, 10 parts
by weight of sugar, 12 parts by weight of a baking powder and 0.5
parts by weight of salt. The product can be readily cooked into a
hot cake having a satisfiable flavor by mixing the product with
water or milk and baking the resultant mixture.
EXAMPLE 10
Ginseng Extract Powder
A half part by weight of ginseng extract was kneaded with 1.5 parts
by weight of an anhydrous crystalline trehalose prepared by the
method in Example for reference 2, and, similarly as in Example 4
the resultant mixture was formed into a block and pulverized to
obtain the captioned product. The product was subjected to a
granulator together with adequate amounts of powdery vitamins B1
and B2 to obtain a granular ginseng extract containing vitamins.
The product can be favorably used as a fatigue-removing agent,
restorative and tonic.
EXAMPLE 11
Solid Preparation for Fluid Food
A composition consisting of 500 parts by weight of an anhydrous
crystalline trehalose prepared by the method in Example for
reference 2, 270 parts by weight of an egg yolk powder prepared by
the method in Example 7, 209 parts by weight of a defatted milk,
4.4 parts by weight of sodium chloride, 1.85 parts by weight of
potassium chloride, 0.01 part by weight of thiamine, 0.1 part by
weight of sodium L-ascorbate, 0.6 parts by weight of vitamin-E
acetate and 0.04 parts by weight of nicotinic acid amide was
prepared, and 25 g aliquots of the composition were injected into
small moistureproof aluminum bags, and heat sealed to obtain the
captioned product.
The product, wherein the moisture content in the atmosphere of the
bag is decreased, does not require cold storage and has a
satisfactory stability for a relatively-long period of time even at
an ambient temperature. The solubility and dispersibility in water
are satisfactory. In use, one bag of the product is dissolved in
about 150-300ml water into a fluid food prior to oral
administration to the body or intubation into the nasal cavity,
stomach and intestine.
EXAMPLE 12
Solid Pharmaceutical Preparation
New born hamsters were injected with an antiserum prepared from
rabbits by conventional method in order to reduce their
immunoreaction, subcutaneously transplanted with BALL-1 cells, and
fed for 3 weeks in usual manner. Subcutaneously-formed tumors in
the hamsters were extracted and cut into pieces which were then
dispersed and suspended in physiological saline. The resultant
cells were washed with RPMI 1640 medium (pH 7.2) free of serum,
resuspened in a fresh preparation of the same medium to give a
concentration of about 2.times.10.sup.6 cells/ml, and kept at
35.degree. C.
To the cell suspension was added 200 IU/ml human
interferon-.alpha., incubated for about 2 hours, mixed with about
300HA (hemagglutination titer)/ml of Sendai virus (HVJ), and
further incubated for 20 hours to induce human interferon-.alpha..
The resultant culture was centrifuged at about 1,000 .times.g and
about 4.degree. C. to remove sediment. The supernatant thus
obtained was membrane filtered, and the resultant filtrate was fed
to a column of an immobilized anti-interferon-.alpha. antibody. The
column was fed with a buffer to remove a non-adsorbed fraction,
followed by eluting an adsorbed fraction from the column and
concentrating the fraction into a solution of about 0.01 w/v %
human interferon-.alpha. having a specific activity of about
2.times.10.sup.8 IU/mg protein in the yield of about 4 ml per
hamster.
Six g aliquots of a pyrogen-free anhydrous crystalline trehalose,
prepared by the method in Example for reference 1, were placed in
100-ml moistureproof plastic bottles, and injected with 0.2 ml
aliquots of the solution containing about 4.times.10.sup.6 IU of
human interferon-.alpha., followed by aseptically capping the
bottles with rubber stoppers and cap-sealing them. Thus, the
captioned product was obtained. According to the preparation, a
solution containing human interferon-.alpha. is simply dehydrated
only by contacting it with a powdery anhydrous trehalose so that
none of treatment, apparatus and energy requisite for general
lyophilization are required, and the human interferon-.alpha. is
effectively stabilized.
The product readily dissolves in water, and this renders it
advantageously useful in an injection for an instillation or an
intramuscular injection as an agent for anti-susceptive diseases
which can be prevented and/or treated with human
interferon-.alpha., for example, an anti-virus agent, anti-tumor
agent and agent of anti-rheumatism. The product can be suitably
used as an internal medicine, as well as an agent for oral cavity.
The product can be also used as a diagnostic reagent.
EXAMPLE 13
Solid Pharmaceutical Preparation
A seed culture of BALL-1 cell derived from human lymphoblastoid was
inoculated into Eagle's minimum essential medium (pH 7.4)
supplemented with 20% fetal calf serum, and subjected to a
suspension culture in vitro at 37.degree. C. in the usual manner.
The resultant cells were washed with serum-free Eagle's minimum
essential medium (pH 7.4), and resuspended in a fresh preparation
of the same medium to give a concentration of about
1.times.10.sup.7 cells/ml. To the cell suspension was added about
1,000 HA/ml of HVJ, and incubated at 38.degree. C. for one day to
induce human tumor necrosis factor-.alpha. (hTNF-.alpha.). The
resultant culture was centrifuged at about 1,000 .times.g and
4.degree. C. to obtain a supernatant which was then dialyzed
against a physiological saline (pH 7.2) containing 0.01M phosphate
buffer for 15 hours, and membrane filtered. The filtrate thus
obtained was fed to a column of an anti-interferon antibody, and a
non-adsorbed fraction was recovered and purified on an affinity
chromatography using a column of an anti-tumor necrosis factor-a
monoclonal antibody, followed by concentrating the resultant into a
0.01 w/v % solution of hTNF-.alpha. having a specific activity of
about 2.times.10.sup.6 JRU (Japan reference unit)/mg protein. The
yield of hTNF-.alpha. was about 5.times.10.sup.4 JRU per one L of
the cell culture.
Ten g aliquots of an anhydrous crystalline trehalose, prepared by
the method in Example for reference 1, were injected into 100-ml
vials which were then injected with 0.5 ml aliquots of the solution
containing about 1.times.10.sup.5 JRU of hTNF-.alpha., aseptically
capped with rubber stoppers, and cap sealed to obtain the captioned
product. Since a solution containing hTNF-.alpha. is dehydrated by
a powdery anhydrous trehalose in the above-mentioned preparation,
no treatment such as a lyophilization is required and hTNF-.alpha.
is effectively stabilized.
The product readily dissolves in water, and this renders it
advantageously useful in an injection for instillation or an
intramuscular injection as an agent for anti-susceptive diseases
which can be prevented and/or treated with hTNF-.alpha., for
example, an anti-virus agent, anti-tumor agent, agent of
anti-ascites and agent of anti-immunopathy. The product can be
suitably used as an internal medicine, as well as an agent for oral
cavity. The product can be also used as a diagnostic reagent.
EXAMPLE 14
Ointment for Treating Skin Trauma
Three parts by weight of iodine was dissolved in 450 parts by
weight of an anhydrous crystalline trehalose prepared by the method
in Example for reference 2, and the solution was admixed with 50
parts by weight of methanol. The resultant solution was admixed
with 200 parts by weight of 10% aqueous pullulan solution and 50
parts by weight of hydrous maltose, and the resultant mixture was
allowed to stand at an ambient temperature overnight to convert the
anhydrous trehalose into hydrous crystalline trehalose. Thus, an
ointment for treating skin trauma having a satisfactory
extensibility and adhesion was obtained.
The product heals trauma such as an ulcer caused by a cut,
abrasion, burn and dermatophytosis. The product exerts the inherent
bactericidal activity of iodine, and acts as a
nutrient-supplementing agent for living cells because it contains
trehalose. Thus, the product shortens a period required for such a
treatment and heals a wounded part thoroughly.
As described above, the present invention relates to a desiccant
comprising a non-reducing anhydrous trehalose as an effective
ingredient. The desiccant can be suitably used to decrease the
moisture content in atmosphere of a moistureproof package injected
with a dehydrated food product, as well as to decrease the moisture
content in a hydrous matter such as food products, pharmaceuticals,
cosmetics, products of chemical engineering, and their materials or
intermediates. The method according to the present invention, which
contains a step of dehydrating a hydrous matter by incorporating
anhydrous trehalose into the hydrous matter to convert the
anhydrous trehalose into hydrous crystalline trehalose, attains a
substantial decrease of the moisture content in the hydrous matter,
and does not require severe conditions such as heat drying. Thus,
high-quality dehydrated products are readily prepared by the
present invention without deteriorating the quality of hydrous
matters such as food products which readily lose their flavors and
tastes, as well as pharmaceuticals which are susceptible to
decomposition and reduction of their effective components. The
dehydrated products thus obtained have a relatively-high stability
and a relatively-long shelf-life because they are prevented from
bacterial contamination, as well as deterioration and alteration
such as hydrolysis, acidification and browning.
While a preferred embodiment of the invention has been illustrative
purpose only, and it is to be understood that changes and
variations may be made without departing from the spirit or scope
of the following claims.
* * * * *